CN1167847C - Sizing composition - Google Patents

Sizing composition Download PDF

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Publication number
CN1167847C
CN1167847C CNB008061688A CN00806168A CN1167847C CN 1167847 C CN1167847 C CN 1167847C CN B008061688 A CNB008061688 A CN B008061688A CN 00806168 A CN00806168 A CN 00806168A CN 1167847 C CN1167847 C CN 1167847C
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CN
China
Prior art keywords
composition
sizing agent
alkyl
ammonium chloride
dimethyl ammonium
Prior art date
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Expired - Fee Related
Application number
CNB008061688A
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Chinese (zh)
Other versions
CN1346417A (en
Inventor
E・林德根
E·林德根
蘩镟
S·弗罗里啻
ǘ
R·斯卡尔
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Akzo Nobel NV
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Akzo Nobel NV
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Publication date
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Publication of CN1346417A publication Critical patent/CN1346417A/en
Application granted granted Critical
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • D21H17/16—Addition products thereof with hydrocarbons
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/17—Ketenes, e.g. ketene dimers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • D21H21/24—Surfactants

Landscapes

  • Paper (AREA)

Abstract

The present invention relates to sizing of paper and more specifically to a substantially water-free and aqueous composition of a sizing agent where the composition contains a cellulose reactive sizing agent, a cationic compound with a molecular weight up to 10000 and a non-ionic compound. Additionally, the invention relates to the preparation and use of above-mentioned compositions.

Description

Glueing composition
The present invention relates to the applying glue of paper, relate more specifically to essentially no water composition and Aquo-composition, its preparation and the purposes of cellulose reactive sizing agent.
Background
Under neutrality or alkalescent raw material pH value, for example the cellulose reactive sizing agent based on alkyl ketene dimer (AKD) and alkenyl succinic anhydrides (ASA) is widely used in papermaking, makes paper and cardboard obtain liquid, aqueous anti-wetting and permeability to a certain degree.Based on the pulp material of cellulose reactive sizing agent generally with comprise water and disperse wherein the sizing agent finely divided particulate or the dispersion form of drop provide.This dispersion is usually utilized by anionic compound such as wooden sodium sulfonate, the dispersant that preferred combination molecular weight amphoteric high or cationic polymer such as cationic starch, polyamine, polyamide or vinyl addition polymer are formed and making.But the dispersion of these types has relatively poor stability and high viscosity usually, even under lower solids content, this obviously causes being difficult to handle this dispersion, for example when storing and use.Another defective is that product must be supplied with the low concentration dispersion, and this has further increased the cost of transportation and the storage cost of reactive gluing agents, because the aqueous components of common dispersion occupies larger volume.
United States Patent (USP) 5176748 relates to the glueing composition of a kind of ASA of comprising, CATION solubility dispersant and dispensable non-ionic surface active agent.Used cation dispersing agent is the high molecular weight cation dispersant, is about 50000 diallyldimethylammonium chloride (Polydadmac) as molecular weight.
EP220941A1 relates to a kind of solid composite that comprises ketenes dimer, encapsulation agent such as polyethers and cationic polymer such as polyamine.
United States Patent (USP) 4743303 discloses the rosin that comprises non-ionic surface active agent and cation dispersing agent and the aqueous dispersion of synthetic sizing agent.
It is emulsion sizing agent that EP707110A1 relates to a kind of alkenyl succinic that comprises emulsifying agent and/or non ionic polymer amount stabilizing agent.
Before using these compositions, they are emulsified in the presence of water.In order to reduce particle diameter, need shearing force.Therefore an advantage of the present invention is to improve the emulsification/dispersion performance.Another advantage of the present invention is to use a kind of good and/or improved glue blending function that obtains when aqueous phase disperses easy/essentially no fast water sizing composition.In addition, the stability problem that relates to conventional size dispersions overcomes by a kind of essentially no water sizing composition is provided.Below provide other purpose.
The present invention
The invention discloses following content:
1. the substantially anhydrous composition of cellulose reactive sizing agent, it is characterized in that this sizing agent is the ketenes dimer, said composition comprise molecular weight be up to 10000 and be selected from contain at least one C9-C30 alkyl primary, the cationic surfactant of secondary, uncle or quaternary ammonium compound, with the non-ionic compound that comprises polyethylene glycol oxide part and aliphatic series part, wherein said composition does not contain rosin and rosin derivative.
2. according to the composition of heading 1, it is characterized in that the dimeric amount of ketenes is at least 50% weight.
3. according to the composition of heading 1, it is characterized in that the amount of described cationic surfactant is the 0.1-20% weight based on sizing agent, and the amount of non-ionic compound is the 0.1-20% weight based on sizing agent.
4. according to the composition of heading 1, it is characterized in that the molecular weight of described cationic surfactant is 200-800.
5. according to the composition of heading 1, it is characterized in that cationic surfactant is selected from general formula R 4The surfactant of N+X-, wherein each R base is independently selected from (i) hydrogen; (ii) C1-C30 alkyl and (iii) by one or more hetero atoms and/or contain heteroatomic group C1-C30 alkyl at interval.
6. according to heading 1,2 or 3 composition, it is characterized in that described cationic surfactant is selected from Quaternium 24, DDAC, dicoco dimethyl ammonium chloride, coconut benzyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, two (octadecyl) alkyl dimethyl ammonium chloride, two (cetyl) alkyl dimethyl ammonium chloride, two (h-tallow) alkyl dimethyl ammonium chloride, two (h-tallow) benzyl ammonio methacrylate, (h-tallow) benzyl dimethyl ammonium chloride, two oil base alkyl dimethyl ammonium chlorides, two (ethylidene hexadecane carboxylic acid ester) alkyl dimethyl ammonium chloride and N-octadecyl-N-dimethyl-N '-trimethyl-propylidene chloride ammoniums.
7. according to the composition of heading 1,2 or 3, it is characterized in that described cationic surfactant is the coconut benzyl dimethyl ammonium chloride through fractionation.
8. according to heading 1,2 or 3 composition, it is characterized in that non-ionic compound comprises polyoxyalkylene part with 5-60 oxyalkylene units and links aliphatic part on the polyoxyalkylene part by ether or ester group, wherein the aliphatic series part is alkyl or the alkenyl that comprises at least 4 carbon atoms.
9. according to the application in the aqueous dispersion of preparation cellulose reactive sizing agent of the composition of heading 1.
10. the method by the substantially anhydrous preparation of compositions aqueous dispersion of heading 1 is characterized in that substantially anhydrous composition is emulsified in the presence of water.
11. composition application in producing paper as raw material sizing agent or Cypres according to heading 1.
12. a papermaking process comprises the substantially anhydrous composition that adds heading 1 in the raw material of cellulose fiber and not essential filler, this raw material is dewatered on the net obtains paper and plain boiled water.
According to the present invention, have been found that utilization according to essentially no water composition of the present invention, can obtain improved homogenization.More particularly, the present invention relates to a kind of essentially no water composition of cellulose reactive sizing agent, comprise the non-ionic compound and the molecular weight that are used as dispersant effectively and be up to 10000 cationic compound.Therefore the easy homogenize of glueing composition of the present invention has reduced the use of shearing force as far as possible.In addition, the present invention relates to a kind of Aquo-composition and preparation and purposes of cellulose reactive sizing agent, further be defined in claims.
The invention enables by getting rid of the water yield often be present in the dispersion effectively and reduce cost of transportation and become possibility.Therefore the present invention has remarkable economical and technical benefits.
Aquo-composition also refers to a kind of aqueous dispersion of cellulose reactive sizing agent.Therefore, aqueous dispersion or Aquo-composition obtain by the emulsification or the homogenization of the essentially no water composition of sizing agent.
Can be selected from any cellulose reactive sizing agent known in the art according to cellulose reactive sizing agent of the present invention.Suitably, sizing agent is selected from hydrophobic ketenes dimer, ketenes polymer, acid anhydrides, organic isocyanate, carbamyl chloride and composition thereof, optimal ethylene ketone dimer and acid anhydrides, most preferably ketenes dimer.Suitable ketenes dimer has following structural formula (I), wherein R 1And R 2Represent saturated or unsaturated alkyl, saturated hydrocarbons normally, described alkyl has 8-36 carbon atom suitably, normally has the straight or branched alkyl of 12-20 carbon atom, as cetyl and octadecyl.Suitable acid anhydrides can be characterized by following general formula (II), wherein R 3And R 4Can be identical or different and can represent to have suitably the saturated or unsaturated alkyl of 8-30 carbon atom or R 3And R 4Can form optionally the 5-6 unit ring that the further alkyl of the highest involved 30 carbon atoms replaces with-C-O-C-part.The example of the acid anhydrides of commercial use comprises alkyl and alkenyl succinic anhydrides, especially different octadecylene base succinyl oxide.
Figure C0080616800071
Suitable ketenes dimer, acid anhydrides and organic isocyanate comprise the compound that is disclosed in United States Patent (USP) 4522686, incorporate it into the present invention as a reference at this.The example of suitable carbamyl chloride is disclosed in those of United States Patent (USP) 3887427, incorporates it into the present invention as a reference at this.
Except the cellulose reactive sizing agent, size dispersions also can comprise the non-cellulose reactive sizing agent.The suitable example of this sizing agent comprises rosin, as fortified rosin and/or esterified rosin, wax, aliphatic acid and resin acid derivative, as fatty acid amide and fatty ester, as the triglycerides of natural acid.
Constitute the cation group that cationic compound of the present invention preferably comprises one or more identical or different kinds, and comprise the cationic compound with a cation group and the cationic compound with two or more cation groups, i.e. cationic polyelectrolyte.The suitable example of cation group comprises the acid-addition salts of sulfonium Ji, Phosphonium base, primary, the second month in a season and tertiary amine or amino and quaternary ammonium group, and for example wherein nitrogen is quaternized by methyl chloride, Dimethylsulfate or benzyl chloride, the acid-addition salts of preferred amines/amino and quaternary ammonium group.The substitution value of cationic polyelectrolyte can change in relative broad range; CATION substitution value (DS C) can be 0.01-1.0.Be 0.1-0.8 suitably, preferred 0.2-0.6.
Be applicable to that CATION organic compound of the present invention comprises the cationic compound that can be used as surfactant and/or dispersant.Preferably, this cationic compound is a kind of surfactant.Cationic surfactant optional self-contained at least one have 9-30 carbon atom alkyl primary, secondary, uncle and quaternary ammonium compound.Further preferred cationic surfactants comprises having general formula R 4N +X -Compound, wherein each R group is independently selected from (i) hydrogen atom; (ii) have about 30 carbon atoms of 1-, the alkyl of preferred 1-22 carbon atom is aliphatic group suitably, preferred alkyl; (iii) have the highest about 30 carbon atoms, preferred 4-22 carbon atom and by the alkyl of one or more hetero atoms such as oxygen or nitrogen interruption is aliphatic group suitably, preferred alkyl, and/or comprise heteroatomic group, as carbonyl or acyloxy; Wherein at least one, preferably at least two described R groups comprise at least 7 carbon atoms, preferably at least 9 carbon atoms, most preferably at least 12 carbon atoms; And X wherein -Be counter ion counterionsl gegenions, normally halogen root such as chlorine root, or be present in group in the counter ion compound of dispersant are to have formula R as surfactant wherein 3The protonated amines of N, wherein R and N definition as above.The example of suitable surfactant comprises Quaternium 24, DDAC, dicoco dimethyl ammonium chloride, coconut benzyl dimethyl ammonium chloride, coconut (fractionation)-benzyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, two (octadecyl) alkyl dimethyl ammonium chloride, two (cetyl) alkyl dimethyl ammonium chloride, two (h-tallow) alkyl dimethyl ammonium chloride, two (h-tallow) benzyl ammonio methacrylate, (h-tallow) benzyl dimethyl ammonium chloride, two oil base alkyl dimethyl ammonium chlorides, with two (ethylidene hexadecane carboxylic acid ester) alkyl dimethyl ammonium chloride.Particularly preferred cationic surfactant comprises those that comprise at least one alkyl with 9-30 carbon atom, especially quaternary ammonium compound.
Further preferred cationic surfactants comprises that comprising at least one has 9-30 carbon atom, and the alkyl of preferred 12-22 carbon atom is aliphatic suitably, the seasonization of preferred alkyl two ammonium compoundss and many ammonium compoundss.The suitable example of this surfactant comprises N-octadecyl-N-dimethyl-N '-trimethyl-propylidene-dichloride two ammoniums.
Be preferred for cationic polyelectrolyte of the present invention and further comprise the low molecular weight cationic organic polymer of degraded optionally, for example derived from those of polysaccharide such as starch and guar gum, CATION condensation product such as cation polyurethane, polyamide such as polyamide-epichlorohydrin copolymer, polyamine such as dimethyl amine-epichlorohydrin copolymer, dimethyl amine-ethylenediamine-epichlorohydrin copolymer, ammonia-dichloroethylene, the vinyl addition polymer that forms by monomer with cation group, as existing as acid-addition salts or quaternary ammonium salt usually, optionally (comprise acrylamide with non-ionic monomer, alkyl acrylate, the derivative of styrene and acrylonitrile and these monomers thereof, vinyl esters and analog) diallyldimethylammonium chloride of copolymerization, propenoic acid dialkyl aminoalkyl ester, the homopolymers and the copolymer of methacrylate and acrylamide (as, the dimethyl aminoethyl ester of acrylic acid and methacrylic acid).
The molecular weight of CATION organic compound is the highest about 10000, and is the highest usually about 5000, the highest suitably by about 3000, preferably the highest about 800.Molecular weight is at least about 200 usually.The molecular weight of suitable cationic surfactants is can be the highest about 3000, and the molecular weight of preferred cationic surfactants is about 200-800.
Be applicable to that non-ionic compound of the present invention comprises the non-ionic compound as surfactant and/or dispersant.Non-ionic compound is polyoxyalkylene ether or polyoxyalkylene esters or its mixture normally.Suitably, non-ionic compound comprises polyoxyalkylene part and aliphatic part.The polyoxyalkylene part of non-ionic compound can comprise a kind of or different oxyalkylene units.Suitably, non-ionic compound comprises at least 3 oxyalkylene units, preferred 4-100, more preferably 5-60 oxyalkylene units, most preferably 5-50 oxyalkylene units.Usually, oxyalkylene units is ethylene oxide or propylene oxide.Usually the aliphatic series part that is keyed to the non-ionic compound on the polyoxyalkylene part by ester or ether group is suitably for branching, linearity or ring-type.Usually, this aliphatic series partly is alkyl or the alkenyl that comprises at least 4 carbon atoms.Suitable non-ionic compound is that ethoxylated fat ether, ethoxylated fat ester or ethoxylated nonylphenol or siloxane glycol polymer are the examples that can be used for compound of the present invention.The example that can be used for preferred non-ionic compound of the present invention is disclosed in Ullman's Encyclopedia of chemical technology(the 5th edition, A25 volume, 783-793 page or leaf); Kirk Othmer chemistry skill The art encyclopedia(the 4th edition, 23 volumes, 506-523 page or leaf) and industrial surface activity agent handbook (the 2nd edition, 1997, Gower Publishing Limited), incorporate it into the present invention as a reference at this.
CATION and non-ionic compound can change in relative broad range according to the amount in essentially no water composition of the present invention and the Aquo-composition, depend on the kind of the kind of CATION and nonionic and charge density, sizing agent, required cationic and dispersions obtained solids content.In essentially no water composition and Aquo-composition, the amount of cationic compound can be based on the highest 100% weight of sizing agent, common 0.1-20% weight, 1-10% weight suitably, preferred 2-7% weight, and the amount of non-ionic compound can be based on the highest 100% weight of sizing agent, common 0.1-20% weight, 0.2-10% weight suitably, preferred 0.3-6% weight.
According to the present invention, glueing composition is anhydrous basically.Basically can there be a spot of water in anhydrous typically referring to; Water content can be a 0-10% weight, is lower than 5% weight suitably, preferably is lower than 2% weight.Most preferably, said composition is anhydrous.
According to a preferred embodiment of the present invention, this essentially no water composition does not have rosin and/or rosin derivative basically." do not have basically " to be meant that the Aquo-composition that obtains comprises rosin and/or the rosin derivative that is lower than 5% weight, is lower than 2% weight suitably after disperseing essentially no water composition.More preferably, this essentially no water composition does not have rosin and/or rosin derivative.
Said composition preferably comprises the cellulose reactive sizing agent of main amount, is base with weight, be suitably at least 50% weight, and the sizing agent content of said composition be 80-99.8% weight suitably, preferably 90-99.7% weight.
According to the present invention, provide to comprise the Aquo-composition that molecular weight is up to the cellulose reactive sizing agent of 10000 cationic compound and non-ionic compound.Aquo-composition of the present invention can be made into highly filled, but still has extraordinary storage stability and low viscosity.Therefore, the invention provides have good and/or improved storage stability, higher solids content and/or more low viscous size dispersions.Another benefit that Aquo-composition of the present invention had is very good and/or improved dilution stability; the low aggregation of this expression sizing agent particle or drop; can form the big aggregation with low applying glue efficient of lower content like this; and the expression low deposition of hydrophobic sizing agent on paper machine and lower network pollution, can reduce curing requirements like this to paper machine.Aquo-composition of the present invention generally has the sizing agent content of about 1-60%.The composition that comprises the ketenes dimer sizing agent according to the present invention can have about 50% weight of 5-, the ketenes dimer content of preferably about 10-35% weight.The dispersion or the emulsion that comprise the acid anhydrides sizing agent according to the present invention can have about 30% weight of 0.1-, the anhydride content of about usually 1-20% weight.
Further shockingly find, according to the essentially no water composition homogenize in the presence of water easily of cellulose reactive sizing agent of the present invention.Compared with the method for the conventional dispersion of preparation, this method needs lower energy and lower shearing force, therefore can adopt the equipment of simplification.Can be according to essentially no water composition of the present invention by the fusing sizing agent and to wherein adding non-ionic compound and cationic compound is made.According to another preferred embodiment, essentially no water composition can be made by melting this sizing agent and adding cationic compound.So the composition that forms is adapted at comprising the aqueous phase emulsification of non-ionic compound subsequently.After the cooling, form the melt solid grain.The Aquo-composition of sizing agent or dispersion can be when heating water suitably and be up to this sizing agent and exist for liquid form temperature, preferably about 20-95 ℃ and obtain.Therefore, another preferred embodiment of the present invention relates to a kind of method for preparing the aqueous dispersion of cellulose reactive sizing agent, the emulsification in the presence of water of wherein essentially no water composition.Another preferred embodiment of the present invention is a kind of method for preparing the aqueous dispersion of cellulose reactive sizing agent, wherein will comprise cellulose reactive sizing agent and the essentially no water sizing composition emulsification in the presence of the water that comprises non-ionic compound with cationic compound of molecular weight the highest 10000.It serves as about 0.1-90% weight to obtain sizing agent content that essentially no water composition of the present invention adds aqueous phase with appropriate amount, the Aquo-composition of preferably about 0.1-50% weight or dispersion.After composition is added water, preferably, form a kind of dispersion like this with formed Aquo-composition emulsification.Glueing composition preferably carries out emulsification in application places or other place of expection.If the dimeric emulsion of preparation ketenes, this method is attractive especially.Therefore the essentially no water sizing composition for preparing stable storing can provide remarkable economical and technical benefits.This essentially no water sizing composition is fit to be mixed with the pellet that can have different shape.
Be present in the component in the present composition, promptly cellulose reactive sizing agent, cationic compound and non-ionic compound preferred definition are as above.
Can use the cellulose fibre of any kind of to be used to produce paper in a usual manner according to composition of the present invention and dispersion, and they can be used for top sizing and inside or raw material applying glue.Term used herein " paper " means and not only comprises paper, and comprises sheet and paper web shape cellulose based product, for example plate and the cardboard of all kinds.Raw material packet cellulose fiber optionally is combined with mineral filler, and the content of cellulose fibre is at least 50% weight based on dried raw material usually.The example of conventional kind mineral filler comprises kaolin, china clay, titanium dioxide, gypsum, talcum and natural and synthetic calcium carbonate such as chalk, crushed marble and winnofil.The invention still further relates to a kind of method of producing paper, the aqueous dispersion that wherein will define as above is used as surface or raw material sizing agent.Suitably, the cellulose reactive sizing agent forms paper or will become the addition in the raw material of Cypres to be the 0.01-1.0% weight based on the dry weight of the not essential filler of cellulose fiber peacekeeping applying (usually under the applying glue press) on the paper surface to the draining on the net that comprises the not essential filler of cellulose fiber peacekeeping, preferred 0.05-0.5% weight, wherein dosage depends primarily on the quality of the paper of the paper pulp or the applying glue of wanting, used cellulose reactive sizing agent and required resin added.
Certainly, the normal chemicals that adds in the raw material can be used in combination with the present composition as retention agent, aluminium compound, dyestuff, wet-strength resins, fluorescent whitening agent etc. in papermaking.The example of aluminium compound comprises alum, aluminate and many aluminium compounds, as polyaluminium chloride and poly aluminium sulfate.The suitable example of retention agent comprises cationic polymer, is combined with the anionic inorganic materials of organic polymer, as be combined with cationic polymer bentonite, be combined with the silica-based sols of cationic polymer or CATION and anionic polymer.But good especially raw material sizing agent the application of the invention Aquo-composition or dispersion and comprise the retention agent of cationic polymer and obtain.Suitable cationic polymers comprises cationic starch, guar gum, acrylate-based and acrylamide-based polymers, polyethylene imine based, dicyandiamide-formaldehyde resin, polyamine, polyamino amine and poly-(diallyldimethylammonium chloride) and combination thereof.Preferred cationic starch and the cation acrylamide based polyalcohol of using, separately or mutually combine or be used in combination with other material.In a preferred embodiment of the invention, dispersion is used in combination with the retention system that comprises at least a cationic polymer and anionic silica-based particles.Aquo-composition of the present invention or dispersion can be before adding one or more cationic polymers, among, add afterwards or simultaneously.Also can be with size dispersions and the retention agent that obtains by essentially no water composition homogenize, carry out premix as cationic polymer such as cationic starch or cation acrylamide based polyalcohol or anionic silica-based material, the mixture that will so obtain then adds in the raw material.Therefore, this Aquo-composition or dispersion can prepare according to essentially no water sizing composition of the present invention by the water emulsifying soln before just adding raw material.
The present invention further specifies by following examples, but is not limited to these.Unless refer else, umber and % relate separately to weight portion and % weight.
Embodiment 1
Applying glue efficient according to moisture glueing composition of the present invention is assessed in this embodiment.The dispersion of AKD is by restraining cationic amine (two (h-tallow) alkyl dimethyl ammonium chlorides with 94.5 gram AKD and 4.0, Querton 442 Akzo Nobel trade names) and 1.5 gram non-ionic compounds (have 7 ethylene oxide units and contain the polyoxyethylene allylic alkylation of the moieties of 11 carbon atoms, Berocell537) fusing and making.This melt solidify to form pellet.Add in 60 ℃ of water 50 these pellets of gram and fusing.Under 15000rpm, use Ultra Turrax blender to prepare this dispersion in 60 seconds.
Prepare page according to being used for breadboard standard method SCAN-C23X.Used paper making raw material comprises 80% bleaching birch and 20% chalk, wherein adds the Na that 0.3 grams per liter is arranged 2SO 410H 2O.The raw material denseness be 0.5% and the pH value be 8.0.This size dispersions is separated the cationic starch that adds raw material and the commercially available retention and the dewatering system CompozilTM of anion aluminium modified silica colloidal sol is used in combination with comprising; The addition of cationic starch is 7 kg/ton based on dried raw material, and the addition of silica sol is that 0.8 kg/ton based on dried raw material is (with SiO 2Meter).
When the addition of AKD was 0.6 kg/ton (calculating with dried raw material), the Cobb value of measuring according to TAPPI normalized thyroxine 41 OS-63 that obtains in test was 17 gram/rice 2This Cobb value representation uses the good paper glue blending function according to glueing composition of the present invention.
Embodiment 2
According to the manufacturing difficulty or ease of dispersion of the present invention by assessing by essentially no water sizing preparation of compositions aqueous dispersion.Dispersion of the present invention is prepared as follows: a) will comprise cationic amine (two (h-tallow) alkyl dimethyl ammonium chloride, Querton 442 Akzo Nobel trade names) and the non-ionic compound of variable quantity (have 7 ethylene oxide units and contain the polyoxyethylene allylic alkylation of the moieties of 11 carbon atoms, Berocell 537) carry out emulsification (test C1-C3), b) the essentially no water composition that will comprise the AKD of cationic amine carries out emulsification, makes that before emulsification the non-ionic compound with the difference amount adds aqueous phase.Assessment comprises the essentially no water sizing composition of the reference according to prior art of AKD and cationic amine (A and B).AKD-wax is used for the present invention, and mixes based on the cationic amine of AKD 2.4% weight with based on the non-ionic compound of AKD 1,2 and 3% weight.
In test C1-C3, non-ionic compound is included in the essentially no water sizing composition.In test D1-D3, non-ionic compound is present in aqueous phase.In test E, assessment comprises AKD, based on the non-ionic compound (Pluronic PE 10500) of comprising of AKD 0.9% weight about 56% propylene oxide and ethylene oxide unit with based on the essentially no water sizing composition of the Polydadmac FL45C of the about 200000-500000 of molecular weight of AKD 0.4% weight.Said composition is dispersed in aqueous phase subsequently.
This anhydrous basically AKD composition adds cationic amine and non-ionic compound or only adds cationic amine by fusing AKD, cools off this melt then and forms solid grain and make.Reference group compound according to prior art is made by the pellet that comprises cationic amine and AKD, and wherein both carry out emulsification (A) subsequently or carry out emulsification (B) in the presence of the water that does not contain sodium naphthalene sulfonate in the presence of the water that comprises sodium naphthalene sulfonate.
Dispersion is by being heated to water about 70 ℃, adds the anhydrous basically AKD composition of pellet form and makes to aqueous phase then.After the adding, operating speed is that the UltraTurrax blender of 15000rpm is used for homogenize/emulsification.Incorporation time changes in second at 5-180.Particle diameter is measured by Malvern Mastersizer.
Table 1
Jitter time, second A B C1 C2 C3 D1 D2 D3 E
5 15 ＞100 8.6 7.3 7.3 7.7 8.6 5.7 4.4
15 6.8 7.5 5.6 5.7 4.8 5.3 4.9 4.3 5.6
30 4.8 5.2 4.3 4.1 2.3 4.6 3.9 3.2 3.3
60 3.7 3.5 3.0 1.9 1.2 2.9 2.5 1.4 4.1
180 1.1 0.8 1.0 0.9 0.7 1.3 0.8 0.7 4.5
Particle diameter is for 50% volume, in micron.
Table 1 shows that by adding non-ionic surface active agent to aqueous phase or in the AKD pellet, obtainable particle diameter descends obviously very fast, has therefore reduced required time and the energy that is used to form dispersion.For E, obtained particle diameter decline faster, but particle diameter never is lower than unacceptable 3.3 microns.

Claims (12)

1. the substantially anhydrous composition of cellulose reactive sizing agent, it is characterized in that this sizing agent is the ketenes dimer, said composition comprise molecular weight be up to 10000 and be selected from contain at least one C9-C30 alkyl primary, the cationic surfactant of secondary, uncle or quaternary ammonium compound, with the non-ionic compound that comprises polyethylene glycol oxide part and aliphatic series part, wherein said composition does not contain rosin and rosin derivative.
2. according to the composition of claim 1, it is characterized in that the dimeric amount of ketenes is at least 50% weight.
3. according to the composition of claim 1, it is characterized in that the amount of described cationic surfactant is the 0.1-20% weight based on sizing agent, and the amount of non-ionic compound is the 0.1-20% weight based on sizing agent.
4. according to the composition of claim 1, it is characterized in that the molecular weight of described cationic surfactant is 200-800.
5. according to the composition of claim 1, it is characterized in that cationic surfactant is selected from general formula R 4N +X -Surfactant, wherein each R base is independently selected from (i) hydrogen; (ii) C1-C30 alkyl and (iii) by one or more hetero atoms and/or contain heteroatomic group C1-C30 alkyl at interval.
6. according to claim 1,2 or 3 composition, it is characterized in that described cationic surfactant is selected from Quaternium 24, DDAC, dicoco dimethyl ammonium chloride, coconut benzyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, two (octadecyl) alkyl dimethyl ammonium chloride, two (cetyl) alkyl dimethyl ammonium chloride, two (h-tallow) alkyl dimethyl ammonium chloride, two (h-tallow) benzyl ammonio methacrylate, (h-tallow) benzyl dimethyl ammonium chloride, two oil base alkyl dimethyl ammonium chlorides, two (ethylidene hexadecane carboxylic acid ester) alkyl dimethyl ammonium chloride and N-octadecyl-N-dimethyl-N '-trimethyl-propylidene chloride ammoniums.
7. according to the composition of claim 1,2 or 3, it is characterized in that described cationic surfactant is the coconut benzyl dimethyl ammonium chloride through fractionation.
8. according to claim 1,2 or 3 composition, it is characterized in that non-ionic compound comprises polyoxyalkylene part with 5-60 oxyalkylene units and links aliphatic part on the polyoxyalkylene part by ether or ester group, wherein the aliphatic series part is alkyl or the alkenyl that comprises at least 4 carbon atoms.
9. according to the application in the aqueous dispersion of preparation cellulose reactive sizing agent of the composition of claim 1.
10. the method by the substantially anhydrous preparation of compositions aqueous dispersion of claim 1 is characterized in that substantially anhydrous composition is emulsified in the presence of water.
11. composition application in producing paper as raw material sizing agent or Cypres according to claim 1.
12. a papermaking process comprises the substantially anhydrous composition that adds claim 1 in the raw material of cellulose fiber and not essential filler, this raw material is dewatered on the net obtains paper and plain boiled water.
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